Nitro dyes, their production and use



United States Patent 3,215,485 NITRO DYES, THEIR PRODUCTION AND USE Otto Senn, Arlesheim, Basel-Land, Switzerland, assignor to Sandoz Ltd. (also known as Sandoz A.G.), Basel, Switzerland No Drawing. Filed Nov. 12, 1963, Ser. No. 323,864 Claims priority, application Switzerland, Nov. 14, 1962, 13,324/62 21 Claims. (Cl. 8-55) It has been found that nitro dyes with good-properties are obtained when a 3-nitr0-4-halogenobenzenesulfonic acid amide is condensed with an aminobenzenecarboxylic acid ester. These starting compounds may be further substituted, preferably by non-wate-r-solubilizing groups.

Esters of the 4-aminosulfonyl-2-nitro-1,1-diphenylamino-2-, -3- or -4'-carboxylic acid, obtained by the above mentioned condensation reaction, are particularly good as disperse dyes for the dyeing of secondary cellulose acetate or cellulose triacetate, or especially of linear aromatic polyesters from aqueous preparations. Being free of water-solubilizing groups they can also be used for the coloration of natural or synthetic resins or plastics or their solutions, of drying oils, viscose, rubber or paper pulp. The dyeings and colorations obtained are outstandingly stable to heat setting and show good fastness to light, washing, water, perspiration, pleating, boiling, acids, alkalis, gas fumes and rubbing. The dyeings on textile fibres are dischargeable. The dyes are suitable for the production of green, brown and grey combination shades using blue anthraquinone dyes as combination elements; these combination dyeings are not subject to catalytic fading.

Preferred dyes of this type are those of the general formula wherein R represents an aliphatic radical with l-6 carbon atoms,

R represents a substituted or unsubstituted hydrocarbon radical, and R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical, or

R together with N and R forms a ring, and

the ring A may contain further substituents, and those of the general formula wherein R represents an aliphatic radical with 1-6 carbon atoms, Y and Y each represent a hydrogen, chlorine or bromine atom, and

the ring A may contain further substituents.

' 3-nitro-4-halogenobenzenesulfonic acid amides which are especially suitable are those of the formula E; (III) wherein X represents a halogen atom, more particularly a chlorine or bromine atom, R represents a substituted or unsubstituted hydrocarbon radical, and R represents 3 ,215,485 Patented Nov. 2, 1965 a hydrogen atom or a substituted or unsubstituted hydrocarbon radical, or R together with N and R forms a ring.

Sulfonamides of the aforenamed type which are either monosubstituted by aryl on the nitrogen atom or monoor disubstituted by alkyl on the nitrogen atom are preferably used. In N-monophenylsulfonamides the phenyl nucleus can be substituted, e.g. by halogen atoms, so that the components used have the formula component is preferably an ester of a 4-aminobenzoic acid with the formula nor-@o 0 OR wherein R represents an aliphatic radical with 1-6 carbon atoms and the ring A may be substituted, e.g. by lowmolecular alkyl groups, preferably in the 2-position to the amino group.

Especially valuable dyes correspond to the formula mooo-QnnG-rn mH (VI) wherein R represents an alkyl radical containing from 1 to 6 carbon atoms,

R represents a secondary to tertiary sulfonic acid amide group, and

n represents a whole number from 0 to 1.

among these may be mentioned a subgroup of the formula NO: /R4 NH s0=N Q Q (VIII) wherein R represents an alkyl radical containing from 1 to 6 carbon atoms,

R represents a member selected from the group consisting of alkyl, monochloro alkyl, monohydroxy alkyl and mono cyano alkyl radical containing from 1 to 6 carbon atoms and of cyclohexyl, phenyl, mono-, diand trimethyl phenyl and monoand dichlorophenyl,

R represents a member selected from the group consisting of hydrogen, alkyl, monochloro, alkyl, monohydroxy alkyl and mono cyano alkyl radical containing from 1 to 6 carbon atoms and of cyclohexyl, phenyl, mono-, diand trimethyl phenyl and monoand dichlorophenyl, and

n represents a whole number from 0 to 1.

In the examples the parts and percentages are by weight and the temperatures are in degrees Centigrade.

3 Example 1 A mixture of 31 parts of 4-chloro-3-nitrobenzene-l-sulfonic acid phenyl amide, 16.5 parts of 4-aminobenzoic acid ethyl ester and 100 parts of crystallized sodium acetate is melted and heated for 10 hours at an oil bath temperature of ISO-160 with stirring and reflux. Subsequently, the yellow melt formed is extracted with 400 parts of hot water. The precipitated dye can be re-crystallized from solution in ethanolr It is then obtained as a yellow crystalline powder of melting point 145. It is suitable for dyeing linear aromatic polyester fibers from aqueous dispersion by heating to 100, maintaining at this temperature for one hour, rinsing and drying. The greenish yellow dyeing obtained has excellent stability to heat setting.

The 4-aminobenzoic acid ethyl ester can be replaced by 15 parts of 4-aminobenzoic acid methyl ester to give a dye of melting point 175 which has similar properties.

Example 2 A mixture of 26.5 parts of 4-chloro3-nitrobenzene-1- sulfonic acid ethylamide, 16.5 parts of 4-aminobenzoic acid ethyl ester, 50 parts of anhydrous sodium acetate and 500 parts of absolute ethanol is stirred for 24 hours at a temperature of 130 in an enameled autoclave. The cold, yellow reaction mass is filtered free from precipitated sodium chloride and the dye is isolated by distillation of the ethanol. The properties of its greenish yellow dyeings on polyester fibers are similar to those of the dye obtained in Example 1.

Example 3 32 parts of 4-chloro-3-nitrobenzene-l-sulfonic acid nhexylamide, 16.5 parts of 4-aminobenzoic acid ethyl ester, 50 parts of calcium carbonate and 3 parts of a dispersing agent are entered into 500 parts of water and boiled with reflux for 8 hours. On cooling, the precipitated dye is filtered oil? and if necessary purified by recrystallization.

Example 4 1 1 1 2 Having thus disclosed the invention what I claim is: '6. The dyestutf 1. Esters of the formula N CH;O-CO- -NH -S0z-NHCH1-CH1CH2-CH R1OOC- NH SOzN 7. The dyestuif 2)IJ NO wherein I CH3 R represents an alkyl radical-containing from 1 to 6 O C carbon atoms, 10 E R represents a member selected from the group consisting of alkyl, monochloroalkyl, monohydroxyal- 8. The dyestufi (n13 CH -0-COC NHSOz-NHCHz-?H CHI 9. The dyestuff 10. The dyestulf l GHQ-CH; 3 G CH3OCO- NH SOz-NH-CH 0H,

GHQ-OH;

kyl and monocyanoalkyl radicals wherein the alkyl 11. The dyestuff moiety contains from 1 to 6 carbon atoms and cyclo- N02 hexyl, R represents a member selected from the group consist- Z ing of hydrogen, alkyl, monochloroalkyl, monohydroxyalkyl and monocyanoalkyl radicals wherein the 12, Th dyestuff alkyl moiety contains from 1 to 6 carbon atoms and cycylohexyl, and

n represents a whole number of from 0 to 1. C H N C y 2. The dyestufi w- 01H;

14. The dyestufi I cm-o-oo-Q-rsnQ-sm-mr-om, No, CH

3 4. The dyestuff G C H3 oni-o-c OO-NHO-SOz-NH-CIHz-ClIa-CH:

15. The dyestufi 5. The dyestutf 16. The dyestutf NO: I OH:

No, I (311: CH=OC O-O-NHQ-SO zNH-CH CgHg-O-C OO-NH-Q-S 0 NH-CH -CH 6E3 (311;

17. The dyestuif CH: oim-o-oo-C -NH--so,NH-c11r-b11 (IJH:

18. The dyestuif 13 14 19. The dyestufi of linear aromatic polyesters which comprises impregnat- I CHZC H2 C H5O-O 0- NH -S0zNH-C /CHQ CH CH 2t)v Process for the production of dyed fiber materials ing the said fiber material with a printing paste containof linear aromatic polyesters which comprises impreging at least one of the dyestuffs of the formula mating the said fiber materials with an aqueous dispersion N02 containing at least one dyestuff of the formula I mooo-QmrQ-m 17702 (CH2) DH wherein R OOC-- NH 1 O R represents an alkyl radical containing from 1 to 6 (011, 11 carbon atoms,

R represents a secondary to tertlary sulforuc acid amide group, and

h i n represents a whole number from 0 to 1.

R represents an alkyl radical containing from 1 to 6 carbon atoms, R represents a secondary to tertiary sulfonic acid amide UNITED STATES PATENTS group, and 2,921,945 1/60 Adams et a1. 260-397] n represents a whole number from 0 to 1. 21. Process for the production of printed fiber materials NORMAN G. TORCHIN, Primary Examiner.

References Cited by the Examiner UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,215,485 November 2, 1965 Otto Senn It is hereb certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

In the grant (only) line 1, for "Otto Sen" read Otto Senn Signed and sealed this 19th day of July 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Comn issioner of Patents Attesting Officer 

20. PROCESS FOR THE PRODUCTION OF DYED FIBER MATERIALS OF LINEAR AROMATIC POLYESTERS WHICH COMPRISES IMPREGNATING THE SAID FIBER MATERIALS WITH AN AQUEOUS DISPERSION CONTAINING AT LEAST ONE DYESTUFF OF THE FORMULA 